Graphite oxide (GO) and graphene monoliths were prepared using the unidirectional freezing of GO water suspension. These materials were saturated with a poly(ammonium-4-styrene sulfonate) water soluble polymer and then carbonized at 1123 K. This process increases significantly the materials strength and density. A uniform deposition of the polymer-derived carbon on the external layers of the graphene sheets of the monolith was found. The carbon from polymer not only provided more contact between the graphene sheets but also apparently increased the overall graphitization level (based on Raman spectra). The modification decreased the electrical resistance by one order of magnitude compared to that of the graphene monolith. N-2 adsorption at 77 K showed that the thus-treated graphene monoliths have quite homogenous pores with the pore width of 0.7 nm. These pores, combined with large transport pores, and conductive properties make the monoliths tested the promising materials for separation, energy storage, and/or gas sensing. The tunability of the properties and pore structure of the robust graphene ultramicroporous monolith through the control of chemistry of the initial GO monolith was shown. (C) 2015 Elsevier Ltd. All rights reserved.